Pd-catalyzed asymmetric Larock reaction for the atroposelective synthesis of N─N chiral indoles

Science Advances, Год журнала: 2024, Номер 10(19)

Опубликована: Май 10, 2024

Atropisomeric indoles defined by a N─N axis are an important class of heterocycles in synthetic and medicinal chemistry material sciences. However, they remain heavily underexplored due to limited methods challenging stereocontrol over the short bonds. Here, we report highly atroposelective access axially chiral via asymmetric Larock reaction. This protocol leveraged powerful role phosphoramidite ligand attenuate common dissociation original reaction, forming with excellent functional group tolerance high enantioselectivity palladium-catalyzed intermolecular annulation between readily available o -iodoaniline alkynes. The multifunctionality prepared allowed diverse post-coupling transformations, affording broad array functionalized indoles. Experimental computational studies have been conducted explore reaction mechanism, elucidating enantio-determining rate-limiting steps.

Язык: Английский

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High‐Throughput Experimentation and Machine Learning‐Assisted Optimization of Iridium‐Catalyzed Cross‐Dimerization of Sulfoxonium Ylides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(48)

Опубликована: Окт. 10, 2023

A novel and convenient approach that combines high-throughput experimentation (HTE) with machine learning (ML) technologies to achieve the first selective cross-dimerization of sulfoxonium ylides via iridium catalysis is presented. variety valuable amide-, ketone-, ester-, N-heterocycle-substituted unsymmetrical E-alkenes are synthesized in good yields high stereoselectivities. This mild method avoids use diazo compounds characterized by simple operation, step-economy, excellent chemoselectivity functional group compatibility. The combined experimental computational studies identify an amide-sulfoxonium ylide as a carbene precursor. Furthermore, comprehensive exploration reaction space also performed (600 reactions) model for yield prediction has been constructed.

Язык: Английский

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Stereoselective Three-Component Carbocyclization of 1,7-Enynes with Sulfoxonium Ylides and Water under Photoredox Catalysis

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6736 - 6741

Опубликована: Июль 29, 2024

A visible-light-induced photoredox three-component carbocyclization reaction of 1,7-enynes with sulfoxonium ylides and water is reported. The protocol provides a facile entry to structurally valuable highly functionalized cyclopenta[c]quinoline scaffolds in chemoselective stereoselective manner. Salient features this method include redox-neutral conditions, no requirement base or other additive, good functional-group tolerance.

Язык: Английский

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Catalytic Asymmetric C–H Activation/Cyclization of Sulfoximines with Sulfoxonium Ylides by a Chiral η⁶-Benzene Ruthenium(II) Catalyst

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 17398 - 17404

Опубликована: Ноя. 12, 2024

Chiral η6-benzene ruthenium(II) (BenRuII)-catalyzed asymmetric C–H activations are challenging and rarely seen in the literature. Herein, activation/cyclization of sulfoximines with sulfoxonium ylides catalyzed by chiral BenRuII catalyst derived from (S)-H8–BINOL is described. It provides efficient access to various sulfur-chiral 1,2-benzothiazine 1-oxides high yields enantioselectivities (up 99% yield 98% ee). Kinetic resolution racemic was also feasible. The reaction mechanism studied tool H/D exchange kinetic isotope effect. metallacycle revealing origin induction prepared, characterized, proved effective for model reaction. This work demonstrates great potential catalysts activation.

Язык: Английский

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Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Язык: Английский

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Planar-chiral arene ruthenium complexes: synthesis, separation of enantiomers, and application for catalytic C–H activation

Chemical Communications, Год журнала: 2024, Номер 60(33), С. 4491 - 4494

Опубликована: Янв. 1, 2024

The enantiomers of an arene ruthenium complex were separated by chromatography using auxiliary chiral phosphine. resolved planar-chiral catalyzed asymmetric C–H activation N -methoxy-benzamides.

Язык: Английский

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High-throughput experimentation and machine learning-promoted synthesis of α-phosphoryloxy ketones via Ru-catalyzed P(O)O-H insertion reactions of sulfoxonium ylides

Science China Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 10, 2024

Язык: Английский

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Recent Advances in the Synthesis of Nitrogen‐Containing Heterocycles Based on Hydrazine‐Directed C−H Bond Activation/Annulation Reactions

European Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract Nitrogen‐containing heterocyclic compounds are the core skeletons of many natural products, bioactive molecules and drugs, transition metal‐catalyzed hydrazine‐directed C−H bond activation/annulation reactions is one effective methods for synthesis nitrogen‐containing compounds. In this review, important research progress activation reviewed according to size constructed heterocycles, substrate scope reaction mechanism discussed in detail, limitations future development prospects summarized outlooked.

Язык: Английский

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Planar chiral arene ruthenium complexes derived from R-carvone

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Natural R -carvone was converted into ruthenium complexes with planar-chiral arene ligands. Similar to the classical [(cymene)RuCl 2 ] complex, they catalyse C–H activation reactions, albeit low stereoselectivity.

Язык: Английский

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Catalyst‐Free Direct Hydrocarbonation of Terminal Alkynes Toward E‐Alkene Substituted Stabilized Sulfoxonium Ylides

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Апрель 2, 2025

Amide and alkene moieties are frequently found in natural products privileged structures pharmaceuticals agrochemicals. Moreover, vinyl sulfoxonium ylide can be converted into a broad range of high-value compounds, thus they have been widely employed organic synthesis. However, the synthesis alkene-substituted amide-sulfoxonium ylides via intermolecular hydrocarbonation alkynes remains underexplored. This study describes development high-throughput approach to provide diverse functionalized E-alkene substituted (hetero)amide-sulfoxonium ylides. The reaction occurs under mild metal-free conditions, employing as highly effective nucleophiles, which participate Michael addition reactions with various alkynes, such esters, thioesters, ketones, amides, sulfones. low-cost, operationally simple has substrate scope, high functional group compatibility, excellent regio- stereoselectivity, making it suitable for transformation structurally complex molecules. Furthermore, obtained stabilized directly useful valuable 1,5-dicarbonyl thiabenzene 1-oxide compounds.

Язык: Английский

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